Mixtures of nanoparticles (NPs) with hybridizing grafted DNA or DNA-like strands have been shown to create highly tunable NP–NP interactions, which, if designed to give nonadditive mixing, could lead ...to a richer self-assembly behavior. While nonadditive mixing is known to result in nontrivial phase behavior in molecular fluids, its effects on colloidal/NP materials have been much less studied. Such effects are explored here via molecular simulations for a binary system of tetrahedral patchy NPs, known to self-assemble into the diamond phase. The NPs are modeled with raised patches that interact through a coarse-grained interparticle potential representing DNA hybridization between grafted strands. It was found that these patchy NPs spontaneously nucleate into the diamond phase, and that hard-interacting NP cores eliminated the competition between the diamond and BCC phases at the conditions studied. Our results also showed that while higher nonadditivity had a small effect on phase behavior, it kinetically enhanced the formation of the diamond phase. Such a kinetic enhancement is argued to arise from changes in phase packing densities and how these modulate the interfacial free energy of the crystalline nucleus by favoring high-density motifs in the isotropic phase and larger NP vibrations in the diamond phase.
Mixtures of nanoparticles (NPs) with hybridizing grafted DNA or DNA-like strands have been of particular interest because of the tunable selectivity provided for the interactions between the NP ...components. A richer self-assembly behavior would be accessible if these NP-NP interactions could be designed to give nonadditive mixing (in analogy to the case of molecular components). Nonadditive mixing occurs when the mixed-state volume is smaller (negative) or larger (positive) than the sum of the individual components’ volumes. However, instances of nonadditivity in colloidal/NP mixtures are rare, and systematic studies of such mixtures are nonexistent. This work focuses on patchy NPs whose patches (coarsely representing grafted hybridizing DNA strands) not only encode selectivity across components but also impart a tunable nonadditivity by varying their extent of protrusion. To guide the exploration of the relationship between phase behavior and nonadditivity for different patches’ designs, the NP–NP potential of mean force (PMF) and a nonadditive parameter were first calculated. For one-patch NPs, different lamellar morphologies were predominantly observed. In contrast, for mixtures of two-patch NPs and (fully grafted) spherical particles, a rich phase behavior was found depending on patch–patch angle and degree of nonadditivity, resulting in phases such as the gyroid, cylinder, honeycomb, and two-layered crystal. Our results also show that both minimum positive nonadditivity and multivalent interactions are necessary for the formation of ordered network mesophases in the class of models studied.
This dissertation discusses nonadditive mixing, which occurs when the volume of a mixed state is either smaller (negative) or larger (positive) than the sum of the volumes of its individual ...components. However, in the context of colloidal and nanoparticle (NP) mixtures, instances of non-additivity are rare, and systematic studies of such mixtures are non-existent. This thesis focuses on investigating nanoparticle non-additive mixing behavior by manipulating the interactions of DNA-chains grafted to them and nanoparticle cores with either non-convex or convex shapes.The first part examines systems containing polyhedra as a baseline and maps their phase diagrams to control negative-mixing behavior. By increasing the extent of shape concavity, the study demonstrates that non-additivity is associated with athermal crystallization of binary mixtures into nanocrystal superlattices.In the second part, the focus is on spherical particles designed to represent highly coarse-grained description of DNA-grafted patchy nanoparticles which are able to exhibit positive-mixing behavior. By varying the patch-patch angle and the degree of non-additivity, a diverse range of phase behaviors is observed in mixtures of two-patch particles and fully grafted spherical particles. These behaviors result in morphologies such as the gyroid, cylinder, honeycomb, and two-layered crystal structures. The findings also reveal that both a minimum positive non-additivity and multivalence of interactions are necessary for the formation of ordered network mesophases in the systems studied.In the second part, the focus is on spherical particles designed to represent highly coarse-grained description of DNA-grafted patchy nanoparticles which are able to exhibit positive-mixing behavior. By varying the patch-patch angle and the degree of non-additivity, a diverse range of phase behaviors is observed in mixtures of two-patch particles and fully grafted spherical particles. These behaviors result in morphologies such as the gyroid, cylinder, honeycomb, and two-layered crystal structures. The findings also reveal that both a minimum positive non-additivity and multivalence of interactions are necessary for the formation of ordered network mesophases in the systems studied.The last study examines mixtures of four-patch nanoparticles with patches arranged with a tetrahedral symmetry to explore how positive non-additivity affects the system’s self-assembly behavior into a crystalline phase with a diamond lattice structure. Our simulations results indicate that higher non-additivity has a minimal effect on phase behavior but enhances the kinetics of formation of the diamond phase.Overall, the text explores non-additive mixing behavior in colloidal and nanoparticle mixtures by manipulating the energetic interactions of the nanoparticle coronas (representing DNA-mediated inter-species selectivity), and the entropy packing interactions of the nanoparticle cores with different shapes. The findings shed light on the relationship between anisotropic interparticle interactions and phase behavior, highlighting the importance of non-additivity and multivalence in the formation of ordered binary compound crystals and network mesophases.
